Intrinsic correlation between the generalized phase equilibrium condition and mechanical behaviors in hydrate-bearing sediments

The phase equilibrium and mechanical behaviors of natural gas hydrate-bearing sediment are essential for gas recovery from hydrate reservoirs.In heating closed systems,the temperature-pressure path of hydrate-bearing sediment deviates from that of pure bulk hydrate,reflecting the porous media effect in phase equilibrium.A generalized phase equilibrium equation was established for hydrate-bearing sediments,which indicates that both capillary and osmotic pressures cause the phase equilibrium curve to shift leftward on the temperature-pressure plane.In contrast to bulk hydrate,hydrate-bearing sediment always contains a certain amount of unhydrated water,which keeps phase equilibrium with the hydrate within the hydrate stability field.With changes in temperature and pressure,a portion of pore hydrate and unhydrated water may transform into each other,affecting the shear strength of hydrate-bearing sediment.A shear strength model is proposed to consider not only hydrate saturation but also the change in temperature and pressure of hydrate-bearing sediment.The model is validated by experimental data with various hydrate saturation,temperature and pressure conditions.The deformation induced by partial dissociation was studied through depressurization tests under constant effective stress.The reduction in gas pressure within the hydrate stability field indeed caused sediment deformation.The dissociation-induced deformation can be reasonably estimated as the difference in volume between hydrate-bearing and hydrate-free sediments from the compression curves.

High-pressure new phases of V–N compounds

The high-pressure diagram of V–N compounds is enriched by proposed seven new stable high-pressure phases.The P-1-VN_4with the armchair N-rich structure may be quenched to ambient conditions.The formed N–N covalent bond plays an important role for the structural stability of N-chain.The charge transfer results in a V–N ionic bond interaction,which further improves the stability of N-chain structure.The P-1-VN_4,P4mnc-VN_8,and Immm-VN_(10)with the outstanding detonation properties have potential application in explosive field.

Effects of high-pressure heat treatment on the solid-state phase transformation and microstructures of Cu_(61.13)Zn_(33.94)Al_(4.93) alloys

The phase transformation activation energy of the Cu61.13Zn33.94A14.93 alloys, which were treated at 4 GPa and 700 ℃ for 15 minutes, was calculated by means of differential scanning calorimetry curves obtained at various heating and cooling rates. Then, the effects of high-pressure heat treatments on the solid-state phase transformation and the microstructures of Cu61.13Zn33.94A14.93 alloys were investigated. The results show that high-pressure heat treatments can refine the grains and can change the preferred orientation from （111） to （200） of α phase. Compared with the as-cast alloy, the sample with high-pressure heat treatment has finer grains, lower β＇→β and/β→β＇ transformation temperature and activation energy. Furthermore, we found that high cooling rate favours the formation of fine needle-like α phase in the range of 5-20℃/min.

An Evaluation of Phase Behaviors of the Oil-Gas-Water System in the Displacement of Crude Oil with CO_(2)

CO_(2)dissolution into an aqueous phase and water evaporation into a gaseous phase takes place during CO_(2)injection into an oil reservoir.This study aims to evaluate the phase behaviors of the oil-gas-water system in the displacement of crude oil by CO_(2).The composition of the JL oilfield in the northeast of China is taken as an example.The flash calculation of the oil-gas-water system was performed,based on the method presented by Li and Nghiem.The research results show that CO_(2)dissolution in the aqueous phase declines as the NaCl concentration in formation water rises.CO_(2)injection is beneficial for the evaporation of formation water.The NaCl concentration in formation water has little effect on water evaporation and dissolved-gas escape.When the injection-gas mole fraction of CO_(2)is 0.5,CO_(2)injection can reverse the phase behavior of the petroleum mixture and the oil-gas system is converted to a pure gas-condensate system.For CO_(2)injection,water vapor has little effect on the miscibility of multiple contacts,but can reduce the miscibility of the first contact.

Elucidating the evolution of long-period stacking ordered phase and its effect on deformation behavior in the as-cast Mg-6Gd-1Zn-0.6Zr alloy

Herein,the evolution of long-period stacking ordered(LPSO)phases in the as-cast Mg-6Gd-1Zn-0.6Zr(wt.%)alloy are investigated via transmission electron microscopy(TEM)and atom probe tomography(APT).The TEM results reveal that two types of LPSO phase(a bulky interdendritic phase and a plate-like matrix LPSO phase)are formed in the as-cast sample.Most of the LPSO phases are confirmed to be of the 14H type,with a smaller proportion being of the 18R LPSO.Further,the APT results reveal that the composition of the interdendritic LPSO phase is closer to that of the ideal 14H phase compared to the matrix LPSO phase,and both the interdendritic and matrix LPSO phases exhibit a Gd/Zn ratio of 2.5,thereby indicating a deficient Zn content compared to the ideal 14H phase(i.e.,1.3).In addition,the influence of the LPSO phases on the deformation behavior is investigated at different compressive plastic strains using electron backscatter diffraction(EBSD)analysis to reveal twinning and slip behavior during deformation.The results indicate that the LPSO phase induces additional work hardening in the late stage of deformation via the suppression of{1011}compressive twinning and the activation of non-basal slip systems.

A transient production prediction method for tight condensate gas wells with multiphase flow

Considering the phase behaviors in condensate gas reservoirs and the oil-gas two-phase linear flow and boundary-dominated flow in the reservoir,a method for predicting the relationship between oil saturation and pressure in the full-path of tight condensate gas well is proposed,and a model for predicting the transient production from tight condensate gas wells with multiphase flow is established.The research indicates that the relationship curve between condensate oil saturation and pressure is crucial for calculating the pseudo-pressure.In the early stage of production or in areas far from the wellbore with high reservoir pressure,the condensate oil saturation can be calculated using early-stage production dynamic data through material balance models.In the late stage of production or in areas close to the wellbore with low reservoir pressure,the condensate oil saturation can be calculated using the data of constant composition expansion test.In the middle stages of production or when reservoir pressure is at an intermediate level,the data obtained from the previous two stages can be interpolated to form a complete full-path relationship curve between oil saturation and pressure.Through simulation and field application,the new method is verified to be reliable and practical.It can be applied for prediction of middle-stage and late-stage production of tight condensate gas wells and assessment of single-well recoverable reserves.

Phase Transitions and Seepage Characteristics during the Depletion Development of Deep Condensate Gas Reservoirs

Deep condensate gas reservoirs exhibit highly complex and variable phase behaviors,making it crucial to understand the relationship between fluid phase states and flow patterns.This study conducts a comprehensive analysis of the actual production process of the deep condensate gas well A1 in a certain oilfield in China.Combining phase behavior analysis and CMG software simulations,the study systematically investigates phase transitions,viscosity,and density changes in the gas and liquid phases under different pressure conditions,with a reservoir temperature of 165°C.The research covers three crucial depletion stages of the reservoir:single-phase flow,two-phase transition,and two-phase flow.The findings indicate that retrograde condensation occurs when the pressure falls below the dew point pressure,reachingmaximum condensate liquid production at around 25MPa.As pressure decreases,gas phase density and viscosity gradually decrease,while liquid phase density and viscosity show an increasing trend.In the initial single-phase flow stage,maintaining a consistent gas-oil ratio is observed when both bottom-hole and reservoir pressures are higher than the dew point pressure.However,a sudden drop in bottom-hole pressure below the dew point triggers the production of condensate oil,significantly reducing subsequent gas and oil production.In the transitional two-phase flow stage,as the bottom-hole pressure further decreases,the reservoir exhibits a complex flow regime with coexisting areas of gas and liquid.In the subsequent two-phase flow stage,when both bottom-hole and reservoir pressures are below the dew point pressure,a significant increase in the gas-oil ratio is observed.The reservoir manifests a two-phase flow regime,devoid of single-phase gas flow areas.For lowpressure conditions in deep condensate gas reservoirs,considerations include gas injection,gas lift,and cyclic gas injection and production in surrounding wells.Additionally,techniques such as hot nitrogen or CO_(2) injection can be employed to mitigate retrograde condensation damage.The implications of this study are crucial for developing targeted development strategies and enhancing the overall development of deep condensate gas reservoirs.

High-Pressure Phase Transitions of PbTe Using the First-Principles Calculations

High-pressure structural phase transitions in PbTe are investigated by means of the first principles total energy calculations within the generalized gradient approximation （GOAl and local density approximation CLDA） by using the density functional theory. First principle calculation shows that PbTe is stable with the NaCl-type （B1） structure under amSient conditions and transforms to the CsCl-type （B2） structure under high pressure via an intermediate phase. Two candidate structures of the intermediate phase, namely Prima and Cmcm, are chosen for total energy calculations and discussed. It indicates that the intermediate phase adopts the Pnma structure rather than the Cmcm structure, and lattice parameters of the Pnma phase calculated by using OGA and LDA are in consistent with experimental results.

Variation of the second-phase morphology and its influence on fracture behavior of Al-Si alloy

Using an optical microscope and scanning electron microscope (SEM), the variation of eutectic Si morphology of Al-Si alloy in solution treatment was observed to study its influence on mechanical properties and fracture behavior. The results show that eutectic Si undergoes stubbing, necking, fragmentation, and growth in the initial stage (250 min); in the middle solution stage (250 to 400 min), the eutectic Si morphology has no significant change, only the degree of spheroidizing becomes higher; after 600 min, the growth of eutectic Si is a coarsening process controlled by diffusion and follows the Liftshitz-Slyozov-Wangner (LSW) model, and the eutectic Si morphology deteriorates due to the occurrence of facets and lap. Based on the quantitative measure and regression analysis, the eutectic Si morphology has a remarkable influence on mechanical properties and fracture behavior.

Phase behavior of TXs/toluene/water microemulsion systems for solubilization absorption of toluene

Triton Xs （TXs） surfactants/cosurfactant/water/oil （toluene） microemulsion systems for enhancing toluene solubilization were proposed and its potential was investigated for toluene removal from gas stream. The results indicated that TX-100 was superior to other TXs surfactants in removing toluene without cosurfactant. The efficiency of cosurfactants for improving toluene solubilization capacity follows the order： amine 〉 alcohol 〉 acid. According to the factor analysis, the linear cosurfactants are better than the branched ones. The effects of hydrophile-lipophile balance （HLB）, salt （NaCl） concentration and temperature on the formation of microemulsion system were also discussed. The results suggested that the optimum value of HLB was 15, the effect of NaCl concentration on the system was inconspicuous and the lower temperature enhanced the solubilization capacity. Nonionic surfactant-based microemulsions had a significant absorption enhancement for toluene, indicated by as much as 82.72% of toluene in phase composition diagram, which will have a great prospect in air pollution treatment.

Influence of high-pressure heat treatment on magnetocaloric effects and magnetic phase transition in single crystal Gd_(3)Ga_5O_(12)

The magnetic properties and magnetic phase transition critical behavior of Gd_(3)Ga_5O_(12)single crystals subjected to high-pressure heat treatment were investigated.The results show that high-pressure heat treatment reduces the Curie temperature and magnetization of the sample.Under a magnetic field change of 5 T,the maximum isothermal magnetic entropy of the sample is approximately 19.73 J/(kg·K).High-pressure heat treatment increases the phase transition temperature range and leads to an increase in the magnetic refrigeration power.Both Gd_(3)Ga_(5)O_(12)single crystals and the high-pressure heat-treated sample undergo a second-order phase transition.The critical behavior of the samples aligns with the mean field model acquired via critical model fitting.This indicates that the samples exhibit long-range exchange interactions in the system near the Curie temperature.Thus,this material can be used as a magnetic refrigerant for low-temperature applications.

Effect of Bimodal Quasicrystal Phase on the Dynamic Recrystallization of Mg–Zn–Gd Alloy during High-Pressure Torsion

The Mg–Zn–Gd alloy with quasicrystal icosahedral phase was processed by high-pressure torsion (HPT). The effect of bimodal I-phase on the dynamic recrystallization was analyzed by transmission electron microscopy. The results showed that the block I-phase can stimulate obvious particle-stimulated nucleation and dynamic recrystallization (DRX) grains were preferentially formed after HPT for 5 turns, while the granular I-phase only promoted the generation of sub-grains. The orientation relationship was determined as twofold//[1210] and fivefold//(0002)_(Mg). Moreover, after HPT for 9 turns, the DRX grains induced by block I-phase appeared to grow up and coarsened. Compared with block I-phase, the grains induced by granular I-phase presented much smaller size and distributed more homogeneous due to the strong pinning effect.

Phase Behavior of Rare Earth Manganites

Among complex oxides containing rare earth and manganese BaLn_2Mn_2O_7 (Ln=rare earth) with the layered perovskite type and Ln_2(Mn, M)O_7 with pyrochlore-related structure were studied since these compounds show many kinds of phases and unique phase transitions. In BaLn_2Mn_2O_7 there appear many phases, depending on the synthetic conditions for each rare earth. The tetragonal phase of so-called Ruddlesden-Popper type is the fundamental structure and many kinds of deformed modification of this structure are obtained. For BaEu_2Mn_2O_7 at least five phases have been identified from the results of X-ray diffraction analysis with the space group P4_2/mnm, Fmmm, Immm and A2/m in addition to the fundamental tetragonal I4/mmm phase. In the pyrochlore-related type compounds, Ln_2Mn_(2-x)M_xO_7 (M=Ta, Nb, W etc), there also appear several phases with different crystal structures. With regard to every rare earth, Ln_2MnTaO_7 phase is stable only for excess Ta and can be obtained under high oxygen partial pressure process. This group has trigonal structure with zirkelite type (P3_121 space group). On the other hand Ln_2Mn_(2/3)Nb_(4/3)O_7 phase has monoclinic (C2/c space group) and zirconolite type structure. All of these structural models have the fundamental structure based on HTB (hexagonal tungsten bronze) layers formed by the arrangement of oxygen octahedra.

Synthesis and Phase Behavior of ω-(cholesteroxycarbonyloxy)-alkyl 3,3,5,5-tetramethyl-3,5-disila-4-oxa cyclohexyl-carboxylate

Four new organosilane compounds containing cholesteryl group were synthesized by esterification of 3,3,5,5-tetramethyl-3,5-disila-4-oxa-cyclohexane-1-carboxylic acid and ω-hydroxyalkyl, cholesteryl carbonate in the presence of DCC and DMAP. Their structures were characterized by1H-NMR, IR and elemental analysis. Their phase behaviors were investigated by differential scanning calorimetry (DSC) and polarized microscopy. Results showed that these four organosilane compounds were all liquid crystalline and longer spacer was advantageous to orientation of organosilane heterocycle and cholesteryl group.

FRACTAL BEHAVIOR OF DEVELOPMENT OF PHASE SEPARATION AND CRYSTALLIZATION IN BLENDS OF NYLON-6 WITH SODIUM SALT OF ETHYLENE /METHACRYLIC ACID COPOLYMER

Phase separation was studied by the optical microscopy in blends of nylon 6 (PA6) with sodium salt of ethylene/methacrylic acid copolymer (PEMA).The image collecting technology was used to keep track of the development of blends at a certain temperature.The fractal dimension of phase separation was calculated by the image solving technology according to the fractal theory and the self similarity behavior of the process was proved.The relationship of the fractal behavior with composition and experimental temperature was discussed.The fractal behavior of the crystallization development of the crystal phase of PA6 in blends was also discussed and the fractal behavior calculated.

Representation of Phase Behavior of Ionic Liquids Using the Equation of State for Square-well Chain Fluids with Variable Range

An equation of state （EOS） for square-well chain fluids with variable range （SWCF-VR） developed based on statistical mechanics for chemical association was employed for the calculations of pressure-volume-temperature （pVT） and phase equilibrium of pure ionic liquids （ILs） and their mixtures. The new molecular parameters for 23 ILs were obtained by fitting their experimental density data over a wide temperature and pressure ranges. The mo- lecular parameters of ILs composed of homologous organic cation and an identical anion such as [Cxmim][NTf2] are good linear with respect to their molecular weight, indicating that the molecular parameters of homologous substances, subsequently p VT and vapor-liquid equilibria vapor-liquid equilibria （VLE） can be predicted using the generalized parameter when no experimental data were available. The new set of parameters were satisfactorily used for calculations of the property of solvent and ILs mixture and the solubility of gas in various ILs at low pressure only using one temperature-independent binary interaction parameter.

Phase Behavior, Thermal Stability and Rheological Properties of PPEK/PC Blends

Phase behavior, thermal stability and rheological properties of the blends of poly(phthalazinone ether ketone) (PPEK) with bisphenol-A polycarbonate (PC) prepared by solution coprecipitation were studied using differential scanning calorimetry (DSC), Frourier-Transform IR spectroscopy (FT-IR), thermogravimetric analysis (TGA) and capillary rheometer. The DSC results indicated that PPEK/PC blends are almost immiscible in full compositions. FT-IR investigation showed that there were no apparent specific interactions between the constituent polymers. The blends keep excellent thermal stability and the addition of PC degrades the thermal stability of blends to some degree. The thermal degradation processes of the blends are much similar to that of PC. The studies on rheological properties of blends show that blending PPEK with PC is beneficial to reducing the melt viscosity and improving the appearance of PPEK.

STUDIES ON STRUCTURE AND PHASE BEHAVIOR OF MULTICOMPONENT POLYMERS THROUGH RHEOLOGICAL TESTS

Rheological measurement has been a preferred approach to the characterization of the structure and phase behaviors for multi-component/multi-phase polymer systems, due to its sensitive response to the changes of structure for these heterogeneous polymers. In the present article, recent progresses in the studies on rheology for heterogeneous polymer systems including phase-separated polymeric blends and block copolymers are reviewed, mainly depending on the results by the authors＇ research group. By means of rheological measurements, not only some new fingerprints responsible for the evolution of morphology and structure concerning these polymer systems are obtained, also the corresponding results are significant for design and preparation of novel polymeric structural materials and functional materials.

Effect of thermodynamic parameters on prediction of phase behavior and process design of extractive distillation

Extractive distillation was investigated for separation of the minimum azeotrope of n-propanol/water, via the Aspen Plus simulation platform. Experimental data of n-propanol/water, which could pass the thermodynamic consistency test, were regressed to get suitable binary interaction parameters(BIPs) by the UNIQUAC thermodynamic model. The azeotrope system was heterogeneous in the simulation with built-in BIPs, which was contrary to the experimental data. The study focused on the effect of thermodynamic parameters on the prediction of phase behavior, and process design of extractive distillation. N-methyl-2-pyrrolidone(NMP) and ethylene glycol were used as solvents to implement the separation. Processes with built-in and regressed BIPs were explored,based on the minimum total annual cost(TAC). There were significant differences in the phase behavior simulation using different thermodynamic parameters, which showed the importance of BIPs in the design and optimization of extractive distillation.

PREDICTION OF THE PHASE BEHAVIOR OF GAS CONDENSATES USING PATEL-TEJA EQUATION OF STATE AND GAMMA DISTRIBUTION FUNCTION

The three-parameter Petal-Teja equation of state coupled with a characterization proceduref0r C7+-fraction based on gamma distribution function was employed to predict the phase behaviorof eight gas condensates.The lumping of the subdivided single carbon number（SCN）hydrocarbons inthe plus-fraction and the choice of empirical correlations for calculating the critical properties andacentric factor of SCN hydrocarbons were discussed.